Bentonite and proteolytic enzyme treatment of beer



Patented Dec. 30, 1 947 BENTONITE AND PROTEOLYTIC ENZYNIE TREATMENT OFBEER Leo Wallerstein, New York, N. Y., assignor to Wallerstein Company,Inc., New York, N. Y., a corporation of New York No Drawing.

Application July 23, 1943,

v Serial-No. 495,846 8 Claims. (CI. 99-48) This invention relates toimprovements in the production of beer.

This application is a continuation, in part, from an abandonedapplication filed February 7, 1938, Serial No. 189,165.

It is to be understood that the term beer is used herein in itscomprehensive sense to include ales and other beverages commonly fallingunder the general classification of beer.

In the production of beer according to gentral practice, an aqueousextract, known as wort, is derived from the mashing of malted cereals.After mashing, the resultant solution is usually filtered from thegrains or other insoluble portions of the mash. In this connection,whenever a filtering process is referred to herein, it is to beunderstood that it includes any equivalent physical process ofseparation. The wort is boiled with hops; the hopped wort in filteredfrom the spent hops; the wort is cooled; and yeast is added to incitefermentation. After this main fermentation, the malt beverage is drawnoff and stored for a considerable time, usually at temperatures around32-40 F., in order that it may ripen and mature. Ordinarily, the beer isfinally filtered before packaging. v

The ripened and matured beer may become draught beer, i. e., beer drawnoff into barrels or kegs for prompt consumption without pasteurizing, orpackaged beer, i. e., beer packaged in bottles, cans or other sealedcontainers and usually pasteurized. The present invention is moreparticularly directed toward packaged beer.

During the period of shelf storage, that is, the period betweenpasteurization and consumption, more or less gradual changes take placein the beer. These changes ordinarily affect the flavor, taste, colorand appearance of the beer, rendering it less desirable and, at times,even unsalable. The extent of change depends on various factors such,for example. as time, temperature, climate, agitation, exposure tolight, the presence of catalysts, etc. The instability thus referred tomay be termed general instability. While many modem beers have had whatmay be considered a fair degree of stability, marketing conditions havegrown more demanding. That is, for example, the shelf life of the beeris often more prolonged and storage and transit conditions moreunfavorable. These factors, together with higher standards, call for ahigher degree of stability. It follows that even today, instabilityremains something of a problem.

The ideal beer should'have such general stability that the changes abovereferred to will not occur to any substantial extent, even under themost adverse conditions. The beer should also have proper foamingqualities and should be chill-proof This last characteristic relates towhat may be considered a special kind of instability. Packaged beers,unless treated, are particularly sensitive to cold. Correctly brewedbeers are originally clear and brilliant but when subjected to chillingtemperatures, such as ice box temperatures, they usually become cloudyor turbid. Treatment to prevent this result is commonly known aschill-proofing.

Various methods for stabilizing and otherwise improving beer have beenproposed from time to time. Among such proposals is the use of certainsilicates of alumina which presumably serve to remove colloidallydissolved albumens of the nature of proteids. An example of suchsilicates is found in the material known as Wyoming bentonite, hereafterreferred to in more detail.

While the use of bentonite in the production of beer has certainadvantages, I have found that its effectiveness as a stabilizing agencyis subject to some limitations. My investigations have shown that as theamount of bentonite used is increased, there is a point at which thebentonite starts to impair the foaming qualities of the beer andadversely affect its taste. Thus a dilemma is encountered. If enoughbentonite is usedto obtain anything like reasonably good stabilization,the beer is apt to have inferior foaming qualities and taste. On theother hand, if the proportion of bentonite is kept small enough to avoidadverse effect on foaming qualities and taste, then the beer willusually lack a desirable degree of stability.

It is an object of the present invention to provide a method ofproducing beer such that a highly stable beer is obtained without dangerof impairing its foaming qualities, taste and other desirablecharacteristics.

More particularly, it is an object of the invention to provide a methodof producing beer that makes possible the use of bentonite and the likeand at the same time avoids the dilemma above referred to.

Other objects and advantages of the invention will be apparent from theensuing description.

I have made the surprising discovery that when both bentonite and anenzymatic preparation are used, under proper conditions, in thepreparation of beer, a superior product may be obtained with only a verysmall proportion of bentonite as compared to the amount considerednecessary should bentonite be used alone. Not only may the proportion ofbentonite used be so small as to avoid substantially all danger that thefoaming qualities and taste of the beer will be impaired, but the beerwill have a high degree of stability. In fact, the stabilization effectwill usually be superior to anything that can be attained by bentonitealone,

regardless of how much bentonite is used.

Other beneficial results of this conjoint use of bentonite and enzymesare hereinafter referred to. I

The material known as Wyoming bentonite is apparently so named becauseit is found in a fairly pure state chiefly in the Fort Benton districtof Wyoming. It is also sometimes known as Volclay and Wilkinite. A

Bentonite is composed chiefly of the mineral montmorillonite andordinarily contains small quantities of other minerals such as feldspar,calcite, quartz, volcanic glass, biolite and zeolite. Montmorillonite isa hydrous silicate of alumina, presumably an alumina-pentasilicate. Arecognized general formula is Other minerals may be present asimpurities.

An average chemical analysis of Wyoming bentonite is as follows:

Wyoming bentonite is characterized, among other things, by its highswelling propensities and its ability to form gels or colloidalsuspensions in thin water dilutions. It consists mainly of particles ofextreme fineness (70% or more finer than 0.5 micron).

If the bentonite is relatively pure, it may be used as mined except thatit is usually preferable to clean it to remove gritty and sandyparticles. While the bentonite may be used in various Ways, I have foundit convenient to add it in the form of an aqueous suspension. Asatisfactory procedure in forming such a suspension is to add bentoniteto water slowly and. in interrupted closes, with agitation following thefinal increment. While the concentration may vary, a 5% to suspensiongives satisfactory results. The aqueous suspension may then be added toth beer under preparation.

The addition of the bentonite may be at various stages in thepreparation of the beer. For-example, the bentonite may be added to thewort after saccharification of the mash and before hopping; or afterhoppin or after main fermentation. The addition of the bentonite shouldbe followed, at some stage, by a filtration or equivalent step. This,however, need not be a special filtration provided that the bentonite isadded at such stage as to be followed by any of the several filtrationsordinarily carried out in the production of the beer.

While the proportional amount of bentonite used may vary, in carryingout the invention to what is now considered the best advantage, I usefrom about 10 grams to about 25 grams of bentonite per barrel of 31gallons. I have found that above 25 grams the foaming qualities andtaste of the beer are apt to start to be impaired and below 10 grams thestabilizing effect is apt to be less than that desired.

As 10 to 25 grams per barrel is approximately only 10% of theproportions heretofore considered necessary were bentonits to be usedalone,

. it is apparent that the conjoint use'of bentonite and an enzymaticpreparation makes possible a great and unexpected saving in material. Itwill also be apparent that the top of the present range is farbelow thebottom of the range considered necessary were bentonite to be usedalone. Consequently, danger of material impairment of foaming qualitiesand taste is substantially eliminated, and without any sacrifice in thestabilization eifect or other results.

The enzymatic preparation used may be any of the enzymes or enzymaticpreparations disclosed in my prior Patents Nos. 995,820, 995,824,995,825, 2,077,447,-2,077,488 and 2,077,449, or any other enzymaticpreparations having the same effect.

In carrying out the invention to what is now considered the bestadvantage, the bentonite and the enzyme should be added separately. Thisavoids any danger that the bentonite will absorb the enzyme and causethe latter to lose efilciency.

The enzymatic preparation should be added after the wort is boiled andcooled inasmuch as high temperatures tend to destroy enzymatic activity.A suitable stage is after main fermentation, e. g. during tank storage.

While the proportional amount of enzymatic preparation used may vary,satisfactory results may be obtained with smaller proportions than thoseprescribed in the patents above referred to. The dosage will varysomewhat, depending on he nature of the materials used. Taking pepsin asan example, about 1 gram of 1:300!) strength pepsin per barrel of 31gallons will give satisfactory results.

A further advantage of the conjoint use of bentonite and enzymes derivesfrom the fact that satisfactory results are obtained with a reducedamount of enzyme as compared to normal chillproofing specifications. Itwill be understood that in the process of the present invention, theenzyme, in addition to whatever other roles it may perform, performs itsusual role of chiliproofing the beer. It is known that in the use ofenzymes for chill-proofing, there is a more or less critical point inthe proportion of enzyme that can be properly used. If the enzyme dosageis too large, deleterious effects may follow. But with the conjoint useof bentonite and enzymes, not only is superior stability obtained withsurprisingly small amounts of bentonite, but, in addition, satisfactorychill-proofing is attained with dosages of enzyme well below anycritical point or range.

The mechanism of whatever inter-relation there may be between theactions of the bentonite and the enzyme in attaining the resultsdescribed is not entirely understood. Nor is it necessary that it shouldbe. The fact remains that when both bentonite and an enzymaticpreparation are used, in accordance with the invention here described,the result is a beer that is highly chillproof and that has a highdegree of general stability. And this result is attained with aproportion of enzyme well below any critical range and a proportion ofbentonite far below the proportion considered necessary to obtain eveninferior stabilization. using bentonite alone, and well below the rangewhere impairment of foaming qualities and taste are apt to result.

It is above stated that both the bentonite and the enzyme may be addedat various stages in attaining the basic advantages of the invention. Ihave found that there are certain supplemental or augmentative and, toan extent, alternative advantages, depending on the stage, the sequenceand other conditions of procedure. The brewer, by selecting the properstage, sequence and the like, may thus obtain the more specific resultshe desires.

For example, if the bentonite portion of the treatment is effected priorto the addition of the enzymatic preparation, the proportion of enzymenecessary to obtain satisfactory results may be reduced verysubstantially below the amount heretofore prescribed for normalchill-proofing. In this respect, addition of the bentonite to the wortand addition of the enzyme after main fermentation have been found togive satisfactory results. With the sequence described, the prior actionof the bentonite presumably eliminates certain substances which wouldotherwise have a deterring effect on the action of the enzyme, wherebyless enzyme is needed. This factor of saving in enzymatic material is'of additional importance from the point of view of expense.

With the sequence just described, particularly advantageous results areobtained if the bentonite portion of the treatment is carried on underelevated temperatures such, for example, as a temperature of around 75C. nection with hopping, will have a temperature of that order in thenatural course, it is convenient to add the bentonite to the hot wort.With such temperatures, the bentonite treatment may be properlyefie'cted in a relatively short time.

By following a different sequence, another supplemental advantage may beattained. It is known that with some beers a fine haze results whenproteolytic enzymes, for chill-proofing, are added to the beer at lowtemperatures, e. g. storage temperatures. This haze appears to be a veryfinely dispersed precipitate. The cause is not entirely understood andthe condition probably varies with the type of malt used. Heretofore, ithas not always been possible to effect a thorough elimination of thishaze. I have found, however,

' that by adding bentonite to the cooled beer after the enzymaticpreparation has been added to the same, this haze may be readily andthoroughly eliminated. Apparently the bentonite provides a flocculatingsurface to permit coagulation and ready removal of the finely dispersedprecipitate. What are now considered the best results are obtained ifthe bentonite is added at least several hours after the enzyme is added.It is noted that when the enzymatic preparation is to be added at thesereduced temperatures, the enzyme used should be one that has analbumen-clotting effect, for example, papain, bromelin or similarenzymes of vegetable origin.

The basic advantges of the invention are attained with either of theseparticular sequences. With the bentonite-enzym sequence the saving inenzymatic material is particularly marked and, if the wort is hot, thereis a substantial saving of time. With the enzyme-bentonite sequence, atcool temperatures, more time is required and the Since the wort, in conaluminum silicates oi the type of montmorillonite,

or materials containing the same in substantial amount and having properswelling propensities and other desirable characteristics, may be used.Of known materials, however, Wyoming bentonite appears to possess thedesirable characteristics in the most favorable degree.

I claim:

1. In the preparation of beer, including mashing material containingmalt to form an extractive wort, causing'saccharification of the mash,separating the wort from the solids present, boiling the wort with theaddition of hops, cooling the wort, causing alcoholic fermentation ofthe hopped wort, storing, and finally filtering prior to packaging, theimprovement which comprises adding, separately, a relatively smallamount of the material commonly known as Wyoming bentonite, in theproportion of from about 10 g. to about 25g. of bentonite per barrel ofbeer, and a relatively small amount of a proteolytic enzymaticpreparation, the bentonite being added at some stage subsequent tosaccharification of the mash and prior to final filtration and theenzymatic preparation being added at some stage subsequent to cooling ofthe wort.

2. In the preparation of beer, including mashing material containingmalt to form an extractive wort, causing saccharification of the mash,separating the wort from the solids present, boiling the wort with theaddition of hops, cooling the wort, causing alcoholic fermentation ofthe hopped wort, storing, and finally filtering prior to packaging, theimprovement which comprises adding, separately, a relatively smallamount of the material commonly known as Wyoming bentonite, in theproportion of from about 10 g. to about 25 g. of bentonite per barrel ofbeer, and a relatively small amount of a proteolytic enzymaticpreparatiomthe bentonite being added at some stage subsequent tosaccharification of the mash and prior to final filtration and theenzymatic preparation being added at some stage subsequent to cooling ofthe wort and subsequent to the addition of the bentonite.

3. In the preparation of beer, including mashing material containingmalt to form an extractive wort, causing saccharification of the mash,separating the wort from the solids present, boiling the wort with theaddition of hops, cooling the wort, causing alcoholic fermentation ofthe hopped wort, storing, and finally filtering prior to packaging, theimprovement which comprises adding a relatively small amount of thematerial v commonly known as Wyoming bentonite to the wort, in theproportion of from about 10 g. to

about 25 g. of bentonite per barrel of wort, andadding a relativelysmall amount of a proteolytic enzymatic preparation subsequent to mainfermentation.

4. In the preparation of beer, including mash- 1 ing material containingmalt to form an extractive wort, causing sacchariflcation of the mash,

a4sa411 ing the wort with the addition of hops, cooling the wort,causing alcoholic fermentation of the hopped wort, storing, and finallyfiltering prior to packaging, the improvement which comprises adding arelatively small amount of the material commonly known as Wyomingbentonite to the wort while hot in the proportion of from about 10 g. toabout 25 g. of bentonite per barrel of wort, and adding a relativelysmall amount of a proteclytic enzymatic preparation subsequent to mainfermentation.

5. In the preparation of beer, including mashing material containingmalt to form an extractive wort, causing saccharifioation of the mash,separating the wort from the solids present, boiling the wort with theaddition of hops, cooling the wort, causing alcoholic fermentation ofthe hopped wort, storing, and finally filtering prior to packaging, theimprovement which comprises adding a relatively small amount of thematerial commonly known as Wyoming bentonite, in the proportion of fromabout 10 g. to about 25 g, of bentonite per barrel of beer, and arelatively small amount of a proteolytic enzymatic preparationsubsequent to main fermentation and at storage temperatures, thebentonite being addeda substantial time-interval after the addition ofthe enzymatic preparation.

6. In the preparation of beer, including mashing material containingmalt to form an extractive wort, causing saccharification of the mash,separating the wort from the solids present, boiling the wort with theaddition of hops, cooling the wort, causing alcoholic fermentation ofthe hopped wort, storing, and finally filtering prior to packaging, theimprovement which comprises adding, separately, the material commonlyknown as Wyomingbentonite and a relatively small amount of a proteolyticenzymatic preparation, the enzymatic preparation being added subsequentto cooling of the wort and the bentonite being added in a proportion offrom about 10 grams to about 25 sramsper barrel of 31 gallons.

7, In the preparation or beer, including mashing material containingmalt to form an extractive wort, causing saccharification of the mash,separating the wort from the solids present, boiling the wort with theaddition of hops, cooling the wort, causing alcoholic fermentation ofthe hopped wort, storing, and finally filtering prior to packaging, theimprovement which comprises adding, separately, a relatively smallamount of a hydrous silicate of alumina of the type 01 montmorillonite,in the proportion oi from about 10 g. to about 25 g. of hydrous silicateof alumina per barrel of beer, and a relatively small amount or aproteolytic" enzymatic preparation, the silicate of alumina being addedat some stage subsequent to saccharification of the mash and prior tofinal filtration and the enzymatic preparation being added at some stagesubsequent to cooling of the wort.

8. In the preparation of beer, the improvement which comprises adding tothe beer, after main fermentation and at storage temperatures, arelatively small amount of a proteolytic enzymatic preparation ofvegetable origin, and thereafter adding a relatively small amount of thematerial commonly known as Wyoming bentonite, in the proportion of fromabout 10 g. to about 25 g. of bentonite per barrel of beer.

LEO WALLERSI'EIN.

REFERENCES CITED The following references are of record in the file ofthis patent:

UNITED STATES PATENTS Number Name Date 2,291,624 Heirnann Aug. 4, 19422,043,713 Saywell June 9, 1936 1,892,457 Cozzolino Dec. 27, 19322,316,241 Heimann Apr. 13, 1943 2,077,446 Wallerstein Apr, 20, 1937

